U.S. patent number 10,112,882 [Application Number 15/514,902] was granted by the patent office on 2018-10-30 for use of novel cyclic carbaldeydes as an aromatic substance.
This patent grant is currently assigned to BASF SE. The grantee listed for this patent is BASF SE. Invention is credited to Richard Dehn, Stephan Maurer, Ralf Pelzer, Joaquim Henrique Teles, Frauke Thrun, Albert Werner.
United States Patent |
10,112,882 |
Thrun , et al. |
October 30, 2018 |
Use of novel cyclic carbaldeydes as an aromatic substance
Abstract
The present invention relates to new types of cyclic
carbaldehydes, the preparation thereof and the use as
aromachemical, in particular as fragrance, and to aroma substance
compositions and products comprising these carbaldehydes.
Inventors: |
Thrun; Frauke (Mannheim,
DE), Teles; Joaquim Henrique (Waldsee, DE),
Werner; Albert (Frankenthal, DE), Dehn; Richard
(Ludwigshafen, DE), Pelzer; Ralf (Furstenberg,
DE), Maurer; Stephan (Neustadt, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
N/A |
DE |
|
|
Assignee: |
BASF SE (Ludwigshafen am Rhein,
DE)
|
Family
ID: |
51625958 |
Appl.
No.: |
15/514,902 |
Filed: |
September 30, 2015 |
PCT
Filed: |
September 30, 2015 |
PCT No.: |
PCT/EP2015/072544 |
371(c)(1),(2),(4) Date: |
March 28, 2017 |
PCT
Pub. No.: |
WO2016/050836 |
PCT
Pub. Date: |
April 07, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20180230076 A1 |
Aug 16, 2018 |
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Foreign Application Priority Data
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Sep 30, 2014 [EP] |
|
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14187075 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C
45/29 (20130101); C11B 9/0038 (20130101); C07C
47/38 (20130101); C07C 45/27 (20130101); C07C
45/27 (20130101); C07C 47/38 (20130101); C07C
45/29 (20130101); C07C 47/28 (20130101); C07C
45/27 (20130101); C07C 47/28 (20130101); C07C
45/29 (20130101); C07C 47/38 (20130101); C07C
2601/18 (20170501) |
Current International
Class: |
C07C
47/38 (20060101); C07C 45/29 (20060101); C11B
9/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1288181 |
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Mar 2003 |
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EP |
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WO-2010086313 |
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Aug 2010 |
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WO |
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WO-2012084673 |
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Jun 2012 |
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WO |
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Other References
"A new sythesis of aldehydes from ketones utilizing", Database
Caplus Accession No. 1994: 434443, XP002736907, 1994. cited by
applicant .
Dory, Y., et al., "On the Mechanism of the Diehls-Alder Reaction of
Enal Dienophiles. Competitive Reactivity and Ab initio Calculations
Using a Transannular Probe", Tetrahedron, 1998, vol. 54, pp.
12279-12288. cited by applicant .
English Translation of International Preliminary Report on
Patentability application No. PCT/EP2015/072544, dated Apr. 6,
2017. cited by applicant .
Ihara, M., et al., A Stereoselective Total ,Synthesis of
(.+-.)-.DELTA..sup.8(12)- Capnellene via the Intramolecular
Diels-Alder Approach, Journal of the Chemical Society, Chemical
Communications, 1991, pp. 646-647. cited by applicant .
Stoll, M., et al., "Contribution a l 'etude des combinaisons
carbocycliques XXX. La Condensation interne de l 'hexadecane-1,
16-dial et de l'octadecane-1, 18 dial", HELV. CHIM. ACTA, 1937,
vol. 20, pp. 525-541. cited by applicant .
Tanzer, E-M., et al., "Fluorinated Organocatalysts for the
Enantioselective Epoxidation of Enals: Molecular Preogranisation by
the Fluorine-Iminium Ion Gauche Effect", Chemistry A European
Journal, 2012, vol. 18, pp. 11334-11342. cited by applicant .
Thommen, C., et al., "Syntheses of Taiwaniaquinone F and
Taiwaniaquinol A via an Unusual Remote C-H Functionalization",
Organic Letters, 2013, vol. 15, No. 16, pp. 1390-1393. cited by
applicant .
International Preliminary Examination Report for PCT/EP2015/072544
(in German) dated Dec. 14, 2016. cited by applicant .
International Search Report for PCT/EP2015/072544 dated Dec. 15,
2015. cited by applicant.
|
Primary Examiner: Witherspoon; Sikarl A
Attorney, Agent or Firm: Drinker Biddle & Reath LLP
Claims
The invention claimed is:
1. A carbaldehyde of the formula X ##STR00021## wherein A is a
cycloaliphatic, monocyclic unsubstituted hydrocarbon radical, the
carbaldehyde selected from isomeric formulae I, II or III,
##STR00022## and the stereoisomeric forms thereof.
2. A composition comprising at least one carbaldehyde according to
claim 1.
3. An aromachemical composition comprising at least one
carbaldehyde of the formula X ##STR00023## wherein A is a
cycloaliphatic, monocyclic, unsubstituted hydrocarbon radical with
15 ring carbon atoms, and n C.dbd.C double bonds, where n is 1, 2
or 3.
4. The aromachemical composition according to claim 3, wherein n is
1.
5. The aromachemical composition according to claim 3, where the
compound is selected from the isomeric compounds of formulae I, II,
or III ##STR00024## and the stereoisomeric forms thereof.
6. A product selected from the group consisting of perfumes,
detergents, cleaners, cosmetic products, body care products,
hygiene articles, foods, food supplements, air fresheners, scent
substances, pharmaceutical products and crop protection products
that contains the aromachemical composition according to claim
3.
7. The aromachemical composition according to claim 3 comprising
trans-cyclopentadec-8-enylcarbaldehyde of the formula (I).
8. The aromachemical composition according to claim 7 further
comprising trans-cyclopentadec-7-enylcarbaldehyde of the formula
(II) and cis-cyclopentadec-8-enylcarbaldehyde of the formula (III),
where the fraction of trans-cyclopentadec-8-enylcarbaldehyde in the
composition, based on a total sum of the formulae I, II and III is
at least 65%.
9. The aromachemical composition according to claim 7 comprising
the compounds of the formulae I, II and III, where the weight ratio
of I:II:III is in the range from 0.3-0.5:0.2-0.3:0.3-0.4.
10. The aromachemical composition according to claim 9, wherein the
weight ratio of I:II:III is about 43:24:33.
11. A process for preparing a compound of formula X ##STR00025##
wherein A is a cycloaliphatic, hydrocarbon radical with in ring
carbon atoms and n C.dbd.C double bonds, where in is an integer
selected from 13, 14, 15, 16 or 17, and n is selected from 1, 2 or
3, where a) reacting a cycloaliphatic compound of the formula XII
##STR00026## wherein A' is a cycloaliphatic hydrocarbon radical
with m+1 ring carbon atoms, where m is an integer selected from 13,
14, 15, 16 or 17, and optionally has n+1 C.dbd.C double bonds,
where n is selected from 1, 2 or 3, with NaH and methyl formate to
give the corresponding cyclic formyl ketone XIII ##STR00027## in
which A' is as defined above; b) reacting the cyclic formyl ketone
with triethylamine and 4-acetamidobenzyl azide to provide the
corresponding diazoketone XIV ##STR00028## in which A' is as
defined above; c) removing the N.sub.2 from the diazoketone under
the conditions in a Wolff rearrangement, N.sub.2 is cleaved off in
the presence of an alkanol to provide the corresponding ester of
formula XV ##STR00029## in which A is as defined above; d) reducing
the ester of formula XV to the corresponding alcohol of formula XVI
##STR00030## in which A is as defined above; e) oxidizing the
alcohol of formula XVI to give the carbaldehyde of the formula X;
and f) optionally, isolating the carbaldehyde of the formula X from
the reaction mixture.
12. The process according to claim 11, wherein the compound of the
formula XII in stage a) is cis-/trans-cyclohexadec-8-enone, and
trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (ii) and
cis-cyclopentadec-8-enylcarbaldehyde (III) are obtained in stage
a).
13. The process according to claim 11, where compounds of the
formulae (I), (II), or (III), or mixtures thereof, are obtained in
stage f) by chromatic purification of a reaction mixture from stage
e), wherein the total amount of (I), (II) and (III) in a mixture
following stage e) is at least 50% by weight.
14. The aromachemical composition according to claim 2 comprising
0.01 to 99.9% by weight of the carbaldehyde of the formula X
##STR00031## wherein A is a cycloaliphatic, monocyclic
unsubstituted hydrocarbon radical, the carbaldehyde selected from
isomeric formulae I, II or III, ##STR00032## and the stereoisomeric
forms thereof, based on the total weight of the composition.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C.
.sctn. 371) of PCT/EP2015/072544, filed Sep. 30, 2015, which claims
benefit of European Application No. 14187075.8, filed Sep. 30,
2014, both of which are incorporated herein by reference in their
entirety.
The present invention relates to new types of cyclic carbaldehydes,
to the preparation thereof and the use as aromachemical, in
particular as fragrance, and to aroma substance compositions and
products comprising these carbaldehydes.
BACKGROUND OF THE INVENTION
In the perfume industry, there is a constant need for new
fragrances which are suitable as fragrance compositions or perfumed
articles. The C.sub.15-aldehydes and the mixtures thereof
constitute a contribution to the expansion of the repertoire in the
fragrance industry, in particular the musk-like fragrances.
In particular, there is a need for musk-like fragrances and
fragrance compositions. This is to be understood as meaning an odor
which is similar to the naturally occurring musk scent.
SUMMARY OF THE INVENTION
Surprisingly, the above object was achieved in particular through
the provision of carbaldehydes of the formula X described below and
primarily through the provision of the specific carbaldehydes of
the following formulae I, II and III, which are notable for a
marked musk scent:
##STR00001##
trans-Cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (III) or mixtures thereof,
called C.sub.15-aldehydes below, are not entirely unknown in the
literature. During the preparation of cyclohexadec-8-en-1-one by
oxidation of cyclohexadec-1,9-diene with nitrous oxide, the
C.sub.15-aldehydes (I), (II) and (III) are produced as byproducts
in a ratio 53:1:44. C.sub.15-Aldehydes (I-Ill) can, moreover, also
be prepared starting from cyclohexadec-8-en-1-one by means of a
multistage synthesis which comprises a Wolff rearrangement. Besides
the already mentioned trans- and cis-C.sub.15-aldehydes (I) and
(III), also the trans-C.sub.15-aldehyde (II) and also the
cis-configuration isomer of (II) are obtained in the process. The
isomer distribution of the isolated product mixture obtained by
Wolff rearrangement is here 43 (I): 24 (II) 33 (III). It has been
found that the C.sub.15-aldehydes (I-III) have very good olfactory
properties. Their odor properties have hitherto not been mentioned
in the literature.
DESCRIPTION OF THE FIGURES
FIG. 1 shows the GC/IR spectra of the compounds I, II and Ill
according to the invention (referred to therein as components 1, 2
and 3).
DETAILED DESCRIPTION OF THE INVENTION
a) General Definitions
An "aroma chemical" is a generic term for compounds which can be
used as "fragrance" and/or as "flavoring".
In the context of the present invention, "fragrance" is to be
understood as meaning natural or synthetic substances with an
intrinsic odor.
In the context of the present invention, "flavoring" is to be
understood as meaning natural or synthetic substances with an
intrinsic taste.
In the context of the present invention, the "odor" or the
"olfactory perception" is the interpretation of the sensory stimuli
which are sent from the chemoreceptors in the nose or other
olfactory organs to the brain of a living being. The odor can
consequently be a sensory perception by the nose of fragrances
which takes place upon breathing in. In this case, the air serves
as the odor carrier.
In the context of the present invention, "scent" is to be
understood as meaning a pleasant smelling odor. The same applies to
a "scent substance" according to the invention.
In the context of the present invention, a "perfume" is a mixture
of fragrances and carriers, such as in particular an alcohol.
In the context of the present invention, a "perfume composition" is
a perfume which comprises different amounts of individual
components matched to one another to be in harmony. The properties
of the individual constituents are utilized in order to provide a
new overall image in the combination, where the characteristics of
the ingredients retire into the background, but without being
suppressed.
In the context of the present invention, a "perfume oil" is a
concentrated mixture of several fragrances which are used e.g. in
alcoholic solutions for the perfuming of various products.
In the context of the present invention, a "scent theme" is the
predominant scent note in a fragrance composition.
In the context of the present invention, the "top note" is the
first phase of the scent progression of a perfume. It plays the
decisive role in the first impression, upon opening the bottle and
when applying the perfume to the skin. The aim of the top note is
to arouse interest in the perfume generally and to ensure
attention. Consequently, an extraordinary character is often more
important than a polished harmony. The top note is naturally
determined by readily volatile fragrances.
In the context of the present invention, "modifying" means to
provide the basic theme of a fragrance composition with additional
or different accords and odor nuances.
In the context of the present invention, "accords" are produced by
combining different fragrances which thus combine to give new odor
images. The number of fragrances used can range from two to several
hundred.
In the context of the present invention, an
"organoleptically/sensorally effective amount" is the amount of a
fragrance which suffices to have a stimulatory effect on a sensory
organ or stimulatory effect on a sensory receptor.
b) Specific Embodiments of the Invention
The present invention relates in particular to the following
subjects: 1. A macrocyclic carbaldehyde of the general formula
X
##STR00002## in which the macrocycle A is a cycloaliphatic
hydrocarbon radical with m ring carbon atoms, where m is a
whole-numbered value from 13 to 17, such as e.g. 13, 14, 15, 16 or
17, in particular 15, and optionally has n C.dbd.C double bonds,
where n is a whole-numbered value of 1, 2 or 3, in particular 1, in
stereoisomerically pure form or in the form of stereoisomer
mixtures, comprising at least two stereoisomeric forms of such a
carbaldehyde; and substance mixtures comprising at least 2, such as
e.g. 2, 3, 4 or 5, in particular 2 or 3, such carbaldehydes in, in
each case, stereoisomerically pure form or as a stereoisomer
mixture. Additionally, preference is given to compounds in which,
in the case of n=1, the carbaldehyde group and the ring C.dbd.C
double bond are 4 to 7 ring carbon atoms apart. Substance mixtures
can, if n is not 0, also comprise constitutional isomers. If n is 2
or 3, then the double bonds are not cumulated. As shown by the
structural formula above, compounds of the formula X are monocyclic
carbaldehydes. Preferably, the compounds of the formula X carry no
further ring substituents on the macrocycle A besides the
carbaldehyde group; it is thus unsubstituted apart from the
carbaldehyde group. 2. The compound according to embodiment 1, in
which n is 1 and/or m is 15, compounds with n=1 and m=15 being
particularly preferred. 3. The compound according to embodiment 2,
selected from the isomeric compounds of the formulae I, II and
III
##STR00003## and the stereoisomeric forms thereof. Preferred
compounds of the formula X are in particular characterized by the
following sets of analytical data:
Set 1:
.sup.1H NMR (500 MHz, CDCl.sub.3, 25.degree. C.): .sigma.=9.5 (s,
CHO, 1H), 5.4-5.3 (m, HC.dbd.CH, 2H), 2.4-2.3 (m, 1H), 2.2-1.9 (m,
4H), 1.7-1.6 (m, 2H), 1.5-1.1 (m, 18H).
.sup.13C-NMR (125 MHz, CDCl.sub.3, 25.degree. C.): 6=206.0
(C.dbd.O), 131.2 (HC.dbd.CH), 48.4 (CH), 31.6 (2.times.CH.sub.2),
28.3 (2.times.CH.sub.2), 27.0 (2.times.CH.sub.2), 26.7
(2.times.CH.sub.2), 26.6 (2.times.CH.sub.2), 25.1
(2.times.CH.sub.2).
IR (GC/IR) .upsilon. [cm.sup.-1]=3029 (1,2 trans subst. DB), 2934,
2865, 2797, 2695, 1738 (CHO), 1454, 1353, 1110, 968 (1,2 trans
subst. DB).
Set 2:
IR (GC/IR) .upsilon. [cm.sup.-1]=3023 (trans 1,2 subst. DB), 2934,
2864, 2801, 2696, 1738 (CHO), 1454, 968 (trans 1,2 subst. DB).
MS (GC/MS-IR coupling) m/z=236.
Set 3:
IR (GC/IR) .upsilon. [cm.sup.-1]=3012 (1,2 cis subst., DB), 2935,
2866, 2801, 2698, 1738 (CHO), 1457, 719 (1,2 cis subst. DB).
MS (GC/MS-IR coupling) m/z=236. The invention thus provides in
particular compounds according to embodiment 2, characterized by
one of the above analytical data sets 1, 2 and 3. Such substances
are e.g. accessible by a process according to the following
embodiments 13 to 17 or by a process of embodiments 18 to 20. The
invention furthermore provides compounds according to embodiments 1
to 3, obtainable according to example 1 and optionally followed by
a purification according to examples 3 and 4 of the experimental
section of the present description. The invention furthermore
provides compounds according to embodiments 1 to 3, obtainable
according to example 2 and optionally followed by a purification
according to examples 3 and 4 of the experimental section of the
present description. The invention furthermore provides compounds
according to embodiments 1 to 3, obtainable according to example 5
(stages 1 to 5) and optionally followed by a purification according
to example 5 (stage 6) of the experimental section of the present
description. 4. A substance mixture comprising at least one, such
as in particular 2, 3 or 4, preferably 2 or 3, compound(s)
according to one of embodiments 1 to 3. Such substance mixtures are
e.g. accessible by a process according to the following embodiments
13 to 17 or by a process of embodiments 18 to 20. The invention
furthermore provides such substance mixtures obtainable by example
1 and optionally followed by a purification according to examples 3
and 4 of the experimental section of the present description. The
invention furthermore provides such substance mixtures obtainable
by example 2 and optionally followed by a purification according to
examples 3 and 4 of the experimental section of the present
description. The invention furthermore provides such substance
mixtures obtainable by example 5 (stages 1 to 5) and optionally
followed by a purification according to example 5 (stage 6) of the
experimental section of the present description. Also encompassed
according to the invention are substance mixtures comprising the
7-cis analogon of the compound of the formula II, i.e.
cis-cyclopentadec-7-enylcarbaldehyde and the use thereof, as
defined herein. Also encompassed according to the invention is the
7-cis analogon of the compound of the formula II, i.e.
cis-cyclopentadec-7-enylcarbaldehyde and the use thereof as defined
herein. 5. The use of at least one substance or substance mixture
according to one of the preceding embodiments as aromachemical, in
particular as fragrance. 6. The use according to embodiment 5 in
products selected from perfumes, detergents and cleaners, cosmetic
products, body care products, hygiene articles, foods, food
supplements, air fresheners, scent substances, pharmaceutical
products and crop protection products. 7. The use according to
either of embodiments 5 and 6 of a mixture essentially comprising
trans-cyclopentadec-8-enylcarbaldehyde (I). 8. The use according to
embodiment 7 of a mixture comprising
trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (III), where the fraction of
trans-cyclopentadec-8-enylcarbaldehyde (I) in the mixture based on
the sum of the components of the formulae I, II and III is at least
65%, such as e.g. 65-100%, 75-98% or 85-95%. 9. The use according
to embodiment 5 or 6 of a mixture comprising the compounds of the
formulae I, II and III, where the weight ratio of I:II:III is in
the range from 0.3-0.5:0.2-0.3:0.3-0.4. 10. The use according to
embodiment 9 of a mixture comprising the compounds of the formulae
I, II and III in a weight ratio of I:II:III of about 43:24:33. 11.
The use according to any one of embodiments 5 to 10 for producing a
musk note in a fragrance composition. 12. The use according to
embodiment 11 for conveying, modifying and/or boosting a musk scent
note in a fragrance composition by admixing a sensorally effective
amount of at least one substance or a substance mixture according
to the definition in any one of embodiments 1 to 10. 13. A process
for the preparation of a compound of the general formula X
##STR00004## in which A is a cycloaliphatic hydrocarbon radical
with m ring carbon atoms, where m is a whole-numbered value from 13
to 17, such as e.g. 13, 14, 15, 16 or 17, in particular 15, and
optionally has n C.dbd.C double bonds, where n is a whole-numbered
value of 1, 2 or 3, where a) a cycloaliphatic compound of the
formula XI
##STR00005## in which A' is a cycloaliphatic hydrocarbon radical
with m+1 ring carbon atoms, where m is a whole-numbered value from
13 to 17, and optionally has n+1 C.dbd.C double bonds, where n is a
whole-numbered value of 1, 2 or 3, in particular 1, which radical
is oxidized with dinitrogen monoxide (N.sub.2O); and b) at least
one compound of the formula X are isolated from the reaction
mixture. 14. The process according to embodiment 13, where the
compound of the formula X is isolated by distillation and
optionally subsequent chromatography. 15. The process according to
embodiment 13 or 14, where the starting material of the formula XI
used is a cyclohexadeca-1,9-diene, and trans- and
cis-cyclopentadec-8-enylcarbaldehyde (I, III) and/or
trans-cyclopentadec-7-enylcarbaldehyde (II) are isolated. 16. The
process according to any one of embodiments 13 to 15, where the
compound of the formulae (I)-(III) is isolated by means of
fractional distillation from a reaction mixture in which the weight
ratio of the C.sub.15-aldehydes (I)-(III) to
cyclohexadeca-1,9-diene is at least 0.01, such as e.g. 0.01-0.1,
0.03-0.095 or 0.06-0.09. 17. The process according to any one of
embodiments 13 to 15, where trans-cyclopentadec-8-enylcarbaldehyde
(I) is isolated by means of chromatic purification from a mixture
which has been obtained by fractional distillation and has a
content of (I)-(III) in total of at least 5% by weight, such as
e.g. 5-50%, 20-48 or 30-45%. 18. A process for the preparation of a
compound of the general formula X
##STR00006## in which A is a cycloaliphatic hydrocarbon radical
with m ring carbon atoms, where m is a whole-numbered value from 13
to 17, and optionally has n C.dbd.C double bonds, where n is a
whole-numbered value of 1, 2 or 3, where a) a cycloaliphatic
compound of the formula XII
##STR00007## in which A' is a cycloaliphatic hydrocarbon radical
with m+1 ring carbon atoms, where m is a whole-numbered value from
13 to 17, such as e.g. 13, 14, 15, 16 or 17, in particular 15, and
optionally has n+1 C.dbd.C double bonds, where n is a
whole-numbered value of 1, 2 or 3, in particular 1, is reacted with
NaH and methyl formate to give the corresponding cyclic
formylketone XIII
##STR00008## in which A' is as defined above, where keto group and
formyl group are preferably bonded to adjacent ring carbon atoms;
b) the formed formylketone is reacted with triethylamine and
4-acetamidobenzyl azide to give the corresponding diazoketone
XIV;
##STR00009## in which A' is as defined above, where keto group and
diazo group are preferably bonded to adjacent ring carbon atoms; c)
N.sub.2 is cleaved off from the formed diazoketone under the
conditions of a Wolff rearrangement and reacted in the presence of
an alcohol to give the corresponding ester of the formula XV
##STR00010## in which A is as defined above; d) the thus formed
ester is reduced to the corresponding alcohol XVI
##STR00011## in which A is as defined above; e) the thus formed
alcohol is oxidized to the carbaldehyde of the formula X; f) and
optionally the carbaldehyde of the formula X is isolated from the
reaction mixture, 19. The process according to embodiment 18, where
cis-/trans-cyclohexadec-8-enone is used as compound of the formula
XI in stage a), and trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (III) are obtained in stage
e). 20. The process according to embodiment 15, where compounds of
the formula (I), (II) or (III) or mixtures thereof are obtained in
stage f) by chromatic purification of a reaction mixture from stage
e), where the content thereof of (I), (II) and (Ill) is in total
preferably at least 50% by weight, such as e.g. 50-100% by weight,
60-99% by weight or 70-95% by weight. 21. A fragrance composition
comprising at least one substance or a substance mixture according
to the definition in any one of embodiments 1 to 10 or prepared by
any one of the processes according to embodiments 13 to 20. 22. The
composition according to embodiment 21, comprising the substance or
the substance mixture in a weight fraction of from 0.01 to 99.9% by
weight, based on the total weight of the composition. 23. A product
comprising at least one substance or a substance mixture according
to the definition in any one of embodiments 1 to 10 or prepared by
any one of the processes according to embodiments 13 to 20. 24. The
product according to embodiment 23, comprising the substance or the
substance mixture in a weight fraction of from 0.01 to 99.9% by
weight, 1 to 80% by weight, 2 to 50% by weight, 3 to 25 or 5 to 15%
by weight, based on the total weight of the composition. 25. The
product according to embodiment 23 or 24, selected from perfumes,
detergents and cleaners, cosmetic products, body care products,
hygiene articles, foods, food supplements, air fresheners, scent
substances, pharmaceutical products and crop protection products.
26. The substance mixture according to embodiment 4, obtainable by
a process according to any one of embodiments 13 to 17 or in
particular 18 to 20.
c) Further Configurations of the Invention
c1) Fragrance Compositions:
According to a further aspect, the fragrances used according to the
invention are used, especially for the purpose of more efficient
handling and metering, also as fragrance mixtures with diluents or
solvents. Here, the fraction of the fragrances, based on the sum of
fragrances and solvents, is given in % by weight.
Solvent:
In the context of the present invention, a "solvent" serves for the
dilution of the fragrances to be used according to the invention or
of the fragrance composition according to the invention without
having its own odiferous properties. Some solvents have fixing
properties at the same time.
The compound of the formula (X) according to the invention or an
above-defined substance mixture of two or more compounds/isomers of
the formula (X) can be admixed to a diluent or solvent in 0.1 to
99% by weight. Preference is given to at least 40% strength by
weight solutions, further preferably at least 50% strength by
weight solutions, furthermore preferably at least 60% strength by
weight solutions, further preferably at least 70% strength by
weight solutions, particularly preferably at least 80% strength by
weight solutions, furthermore particularly preferably at least 90%
strength by weight solutions, preferably in olfactorily acceptable
solvents.
Preferred olfactorily acceptable solvents are ethanol, dipropylene
glycol (DPG), propylene glycol, 1,2-butylene glycol, glycerol,
diethylene glycol monoethyl ether, diethyl phthalate (DEP),
isopropyl myristate (IPM), triethyl citrate (TEC), benzyl benzoate
(BB) and benzyl acetate. Here, preference is in turn given to
ethanol, diethyl phthalate, propylene glycol, dipropylene glycol,
triethyl citrate, benzyl benzoate and isopropyl myristate.
In the context of the present invention, a "fragrance composition"
is a mixture which comprises at least one further fragrance
alongside a compound of the formula (X) according to the invention
or an above-defined substance mixture of two or more
compounds/isomers of the formula (X). In particular, such a
fragrance composition can be a perfume composition (a perfume
oil).
Fragrance compositions according to the invention comprise, based
on the total amount of the fragrance composition, e.g. an amount of
a compound of the formula (X) according to the invention or of an
above-defined substance mixture of two or more compounds/isomers of
the formula (X) of from 0.01 to 65% by weight, preferably from
about 0.1 to about 50% by weight, preferably from about 0.5 to
about 30% by weight and particularly preferably from about 0.5 to
about 25% by weight. The weight ratio of compound/compounds of the
formula X according to the invention to the total amount of further
fragrances is e.g. in the range from 1:1000 to 1:0.5, preferably in
the range from 1:700 to 1:1, particularly preferably in the range
from 1:500 to 1:10.
Fragrance compositions according to the invention comprise, based
on the total amount of the fragrance composition, e.g. an amount of
compound/compounds of the formula X according to the invention of
from 0.01 to 65% by weight, preferably from about 0.1 to about 50%
by weight, preferably from about 0.5 to about 30% by weight and
particularly preferably from about 0.5 to about 25% by weight. The
weight ratio of compound/compounds of the formula X according to
the invention to the total amount of further fragrances (different
therefrom) is e.g. in the range from 1:1000 to 1:0.5, preferably in
the range from 1:700 to 1:1, particularly preferably in the range
from 1:500 to 1:10.
Further Fragrances:
Besides the compound/compounds of the formula X according to the
invention, fragrance compositions according to the invention
comprise at least one further fragrance, preferably 2, 3, 4, 5, 6,
7, 8 or more further fragrances, where further fragrances are
selected e.g. from among:
Alpha-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate
(Phenirat.sup.1), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol),
methyl dihydrojasmonate (preferably with a content of cis isomer of
more than 60% by weight) (Hedione.sup.9, Hedione HC.sup.9),
4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]benzopyran
(Galaxolid.sup.3), tetrahydrolinalool (3,7-dimethyloctan-3-ol),
ethyllinalool, benzyl salicylate,
2-methyl-3-(4-tert-butylphenyl)propanal (Lilial.sup.2), cinnamyl
alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate
and/or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate
(Herbaflorat.sup.1), citronellol, citronellyl acetate,
tetrahydrogeraniol, vanillin, linalyl acetate, styrolyl acetate
(1-phenylethyl acetate),
octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and/or
2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene
(Iso E Super.sup.3), hexyl salicylate, 4-tert-butylcyclohexyl
acetate (Oryclone.sup.1), 2-tert-butylcyclohexyl acetate (Agrumex
HC.sup.1), alpha-ionone
(4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one),
n-alpha-methylionone, alpha-isomethylionone, coumarin, terpinyl
acetate, 2-phenylethyl alcohol,
4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde
(Lyral.sup.3), alpha-amylcinnamaldehyde, ethylene brassylate, (E)-
and/or (Z)-3-methylcyclopentadec-5-enone (Muscenon.sup.9),
15-pentadec-11-enolide and/or 15-pentadec-12-enolide
(Globalide.sup.1), 15-cyclopentadecanolide (Macrolide'),
1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone
(Tonalid.sup.10), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol
(Florol.sup.9),
2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol
(Sandolen.sup.1), cis-3-hexenyl acetate, trans-3-hexenyl acetate,
trans-2/cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde
(Vertocitral.sup.1), 2,4,4,7-tetramethyloct-6-en-3-one
(Claritone.sup.1), 2,6-dimethyl-5-hepten-1-al (Melonal.sup.2),
borneol, 3-(3-isopropylphenyl)butanal (Florhydral.sup.2),
2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional.sup.3),
3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon.sup.1),
7-methyl-2H-1,5-benzodioxepin-3(4H)-one (Calone.sup.19515),
3,3,5-trimethylcyclohexyl acetate (preferably with a content of cis
isomers of 70% by weight or more) and
2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol
S.sup.1). Within the context of the present invention, the
aforementioned fragrances are accordingly preferably combined with
mixtures according to the invention.
Where trade names are given above, these refer to the following
sources:
.sup.1 trade name of Sym rise GmbH, Germany;
.sup.2 trade name of Givaudan AG, Switzerland;
.sup.3 trade name of International Flavors & Fragrances Inc.,
USA;
.sup.5 trade name of Danisco Seillans S.A., France;
.sup.9 trade name of Firmenich S.A., Switzerland;
.sup.10 trade name of PFW Aroma Chemicals B.V., the
Netherlands.
Further fragrances with which the
(E/Z)-cyclopentadecenylcarbaldehydes (I)-(III) can be combined e.g.
to give a fragrance composition can be found e.g. in S. Arctander,
Perfume and Flavor Chemicals, Vol. I and II, Montclair, N.J., 1969,
self-published, or K. Bauer, D. Garbe and H. Surburg, Common
Fragrance and Flavor Materials, 4th Ed., Wiley-VCH, Weinheim 2001.
Specifically, mention may be made of:
extracts from natural raw materials such as essential oils,
concretes, absolutes, resins, resinoids, balsams, tinctures such as
e.g.
ambergris tincture; amyris oil; angelica seed oil; angelica root
oil; aniseed oil; valerian oil; basil oil; tree moss absolute; bay
oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute;
birch tar oil; bitter almond oil; savory oil; buchu leaf oil;
cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil;
cardamom oil; cascarilla oil; cassia oil; cassia absolute;
castoreum absolute; cedar leaf oil; cedar wood oil; cistus oil;
citronella oil; lemon oil; copaiba balsam; copaiba balsam oil;
coriander oil; costus root oil; cumin oil; cypress oil; davana oil;
dill weed oil; dill seed oil; Eau de brouts absolute; oak moss
absolute; elemi oil; tarragon oil; eucalyptus citriodora oil;
eucalyptus oil; fennel oil; spruce needle oil; galbanum oil;
galbanum resin; geranium oil; grapefruit oil; guaiacwood oil;
gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum
oil; ginger oil; iris root absolute; iris root oil; jasmine
absolute; calmus oil; camomile oil blue; roman camomile oil; carrot
seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway
oil; labdanum oil; labdanum absolute; labdanum resin; lavandin
absolute; lavandin oil; lavender absolute; lavender oil; lemongrass
oil; lovage oil; lime oil distilled; lime oil pressed; linalool
oil; litsea cubeba oil; laurel leaf oil; mace oil; marjoram oil;
mandarin oil; massoia bark oil; mimosa absolute; musk seed oil;
musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh
oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil;
olibanum absolute; olibanum oil; opopanax oil; orange blossom
absolute; orange oil; origanum oil; palmarosa oil; patchouli oil;
perilla oil; peru balsam oil; parsley leaf oil; parsley seed oil;
petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil;
pennyroyal oil; rose absolute; rose wood oil; rose oil; rosemary
oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery
seed oil; spike-lavender oil; star anise oil; styrax oil; tagetes
oil; fir needle oil; tea tree oil; turpentine oil; thyme oil;
tolubalsam; tonka absolute; tuberose absolute; vanilla extract;
violet leaf absolute; verbena oil; vetiver oil; juniper berry oil;
wine lees oil; wormwood oil; winter green oil; ylang ylang oil;
hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil,
and fractions thereof, or ingredients isolated therefrom;
individual fragrances from the group of hydrocarbons, such as e.g.
3-carene; alpha-pinene; beta-pinene; alpha-terpinene;
gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene;
cedrene; farnesene; limonene; longifolene; myrcene; ocimene;
valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane; the
aliphatic alcohols such as e.g. hexanol; octanol; 3-octanol;
2,6-dimethylheptanol; 2-methyl-2-heptanal; 2-methyl-2-octanol;
(E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of
3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and
3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol;
3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol;
4-methyl-3-decen-5-ol; the aliphatic aldehydes and acetals thereof
such as e.g. hexanal; heptanal; octanal; nonanal; decanal;
undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal;
(E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal;
10-undecenal; (E)-4-decenal; 2-dodecenal;
2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal;
heptanal diethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene;
citronellyloxyacetaldehyde; (E/Z)-1-(1-methoxypropoxy)-hex-3-ene;
the aliphatic ketones and oximes thereof such as e.g. 2-heptanone;
2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone;
5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one;
6-methyl-5-hepten-2-one; the aliphatic sulfur-containing compounds
such as e.g. 3-methylthiohexanol; 3-methylthiohexyl acetate;
3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl
butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; the
aliphatic nitriles such as e.g. 2-nonenenitrile; 2-undecenenitrile;
2-tridecenenitrile; 3,12-tridecadienenitrile;
3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;
the esters of aliphatic carboxylic acids such as e.g. (E)- and
(Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl
acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate;
(E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl
acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate;
butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and
(Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate;
ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl
heptanoate; allyl heptanoate; ethyl octanoate; ethyl
(E,Z)-2,4-decadienoate; methyl 2-octinate; methyl 2-noninate; allyl
2-isoamyloxy acetate; methyl-3,7-dimethyl-2,6-octadienoate;
4-methyl-2-pentyl crotonate; the acyclic terpene alcohols such as
e.g. geraniol; nerol; linalool; lavandulol; nerolidol; farnesol;
tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol;
2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol;
2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol;
3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol;
2,6-dimethyl-2,5,7-octatrien-1-ol; and the formates, acetates,
propionates, isobutyrates, butyrates, isovalerates, pentanoates,
hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates
thereof; the acyclic terpene aldehydes and ketones such as e.g.
geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal;
7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal;
geranyl acetone; as well as the dimethyl- and diethylacetals of
geranial, neral, 7-hydroxy-3,7-dimethyloctanal; the cyclic terpene
alcohols such as e.g. menthol; isopulegol; alpha-terpineol;
terpine-4-ol; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol;
isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol;
guajol; and the formates, acetates, propionates, isobutyrates,
butyrates, isovalerates, pentanoates, hexanoates, crotonates,
tiglinates and 3-methyl-2-butenoates thereof; the cyclic terpene
aldehydes and ketones such as e.g. menthone; isomenthone;
8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone;
beta-ionone; alpha-n-methylionone; beta-n-methylionone;
alpha-isomethylionone; beta-isomethylionone; alpha-irone;
alpha-damascone; beta-damascone; beta-damascenone; delta-damascone;
gamma-damascone;
1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;
1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalene-8(5-
H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal;
nootkatone; dihydronootkatone; 4,6,8-megastigmatrien-3-one;
alpha-sinensal; beta-sinensal; acetylated cedar wood oil (methyl
cedryl ketone); the cyclic alcohols such as e.g.
4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol;
3-isocamphylcyclohexanol;
2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol;
2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; the cycloaliphatic
alcohols such as e.g. alpha-3,3-trimethylcyclohexylmethanol;
1-(4-isopropylcyclohexyl)ethanol;
2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol;
2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-01;
2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol;
3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol;
3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;
3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;
1-(2,2,6-trimethylcyclohexyl)pentan-3-ol;
1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; the cyclic and
cycloaliphatic ethers such as e.g. cineol; cedryl methyl ether;
cyclododecyl methyl ether; 1,1-dimethoxycyclododecane;
(ethoxymethoxy)cyclododecane; alpha-cedrene epoxide;
3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan;
3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan;
1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide;
2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxan-
e; the cyclic and macrocyclic ketones such as e.g.
4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone;
2-heptylcyclopentanone; 2-pentylcyclopentanone;
2-hydroxy-3-methyl-2-cyclopenten-1-one;
3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one;
3-methyl-2-pentyl-2-cyclopenten-1-one;
3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone;
3-methylcyclopentadecanone;
4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;
4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one;
6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;
8-cyclohexadecen-1-one; 7-cyclohexadecen-1-one;
(7/8)-cyclohexadecen-1-one; 9-cycloheptadecen-1-one;
cyclopentadecanone; cyclohexadecanone; the cycloaliphatic aldehydes
such as e.g. 2,4-dimethyl-3-cyclohexenecarbaldehyde;
2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde;
4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; the
cycloaliphatic ketones such as e.g.
1-(3,3-dimethylcyclohexyl)-4-penten-1-one;
2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone;
1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;
2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl
ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone;
tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone; the esters of
cyclic alcohols such as e.g. 2-tert-butylcyclohexyl acetate;
4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate;
4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate;
decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate;
3-pentyltetrahydro-2H-pyran-4-yl acetate;
decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate;
4,7-methanooctahydro-5 or 6-indenyl acetate; the esters of
cycloaliphatic alcohols such as e.g. 1-cyclohexylethyl crotonate;
the esters of cycloaliphatic carboxylic acids such as e.g. allyl
3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and
trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate;
methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl
2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl
2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl
2-methyl-1,3-dioxolane-2-acetate; the araliphatic alcohols such as
e.g. benzyl alcohol; 1-phenylethyl alcohol, 2-phenylethyl alcohol,
3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol;
2,2-dimethyl-3-phenylpropanol;
2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl
alcohol; 1,1-dimethyl-3-phenylpropanol;
1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol;
3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl
alcohol; 1-(4-isopropylphenyl)ethanol; the esters of araliphatic
alcohols and aliphatic carboxylic acids such as e.g. benzyl
acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate;
2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl
isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate;
alpha-trichloromethylbenzyl acetate;
alpha,alpha-dimethylphenylethyl acetate;
alpha,alpha-dimethylphenylethyl butyrate; cinnamyl acetate;
2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the
araliphatic ethers such as e.g. 2-phenylethyl methyl ether;
2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether;
phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl
acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde
glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane;
4,4a,5,9b-tetrahydroindeno[1,2-d]m-dioxine;
4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine; the
aromatic and araliphatic aldehydes such as e.g. benzaldehyde;
phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde;
4-methylbenzaldehyde; 4-methylphenylacetaldehyde;
3-(4-ethylphenyl)-2,2-dimethylpropanal;
2-methyl-3-(4-isopropylphenyl)propanal;
2-methyl-3-(4-tert-butylphenyl)propanal;
2-methyl-3-(4-isobutylphenyl)propanal;
3-(4-tert-butylphenyl)propanal; cinnamaldehyde;
alpha-butylcinnamaldehyde; alpha-amylcinnamaldehyde;
alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal;
4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde;
4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde;
3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal;
2-methyl-3-(4-methylenedioxyphenyl)propanal; the aromatic and
araliphatic ketones such as e.g. acetophenone;
4-methylacetophenone; 4-methoxyacetophenone;
4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone;
4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone;
2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone;
benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone;
6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone;
1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanon-
e;
5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone;
the aromatic and araliphatic carboxylic acids and esters thereof
such as e.g. benzoic acid; phenylacetic acid; methyl benzoate;
ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl
phenylacetate; ethyl phenylacetate; geranyl phenylacetate;
phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate;
benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl
phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl
salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl
salicylate; phenylethyl salicylate; methyl
2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl
3-methyl-3-phenylglycidate; the nitrogen-containing aromatic
compounds such as e.g.
2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene;
3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile;
3-methyl-5-phenyl-2-pentenonitrile;
3-methyl-5-phenylpentanenitrile; methyl anthranilate;
methyl-N-methylanthranilate; Schiff bases of methyl anthranilate
with 7-hydroxy-3,7-dimethyloctanal,
2-methyl-3-(4-tert-butylphenyl)propanal or
2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline;
6-isobutylquinoline; 6-sec-butylquinoline;
2-(3-phenylpropyl)pyridine; indole; skatole;
2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; the
phenols, phenyl ethers and phenyl esters such as e.g. estragole;
anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl
methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl
methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl
ether; 1,4-dimethoxybenzene; eugenyl acetate;
2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl
phenylacetate; the heterocyclic compounds such as e.g.
2,5-dimethyl-4-hydroxy-2H-furan-3-one;
2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one;
3-hydroxy-2-methyl-4H-pyran-4-one;
2-ethyl-3-hydroxy-4H-pyran-4-one; the lactones such as e.g.
1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide;
1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide;
1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide;
4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis- and
trans-11-pentadecen-1,15-olide; cis- and
trans-12-pentadecen-1,15-olide; 1,16-hexadecanolide;
9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide;
11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene
1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin;
2,3-dihydrocoumarin; octahydrocoumarin. c2) Fragrance-Containing
Articles
Cyclopentadecenylcarbaldehydes of the formulae (I)-(III) according
to the invention or fragrance compositions according to the
invention can be incorporated into a series of products or be
applied to such products.
Fragrances according to the invention can be used in the production
of perfumed articles. The olfactory properties, like the material
properties (such as solubility in customary solvents and
compatibility with further customary constituents of such
products), as well as the toxicological acceptability of the
fragrances according to the invention underline their particular
suitability for the stated use purposes. The positive properties
contribute to the fact that the fragrances used according to the
invention and the fragrance compositions according to the invention
are particularly preferably used in perfume products, body care
products, hygiene articles, textile detergents, and in cleaners for
solid surfaces.
The perfumed article is e.g. selected from perfume products, body
care products, hygiene articles, textile detergents and cleaners
for solid surfaces. Preferred perfumed articles according to the
invention are also selected from among:
perfume products selected from perfume extracts, Eau de Parfums,
Eau de Toilettes, Eau de Colognes, Eau de Solide, Extrait Partum,
air fresheners in liquid form, gel-like form or a form applied to a
solid carrier, aerosol sprays, scented cleaners and oils;
body care products selected from aftershaves, pre-shave products,
splash colognes, solid and liquid soaps, shower gels, shampoos,
shaving soaps, shaving foams, bath oils, cosmetic emulsions of the
oil-in-water type, of the water-in-oil type and of the
water-in-oil-in-water type, such as e.g. skin creams and lotions,
face creams and lotions, sunscreen creams and lotions, aftersun
creams and lotions, hand creams and lotions, foot creams and
lotions, hair removal creams and lotions, aftershave creams and
lotions, tanning creams and lotions, hair care products such as
e.g. hairsprays, hair gels, setting hair lotions, hair
conditioners, hair shampoo, permanent and semipermanent hair
colorants, hair shaping compositions such as cold waves and hair
smoothing compositions, hair tonics, hair creams and hair lotions,
deodorants and antiperspirants such as e.g. underarm sprays,
roll-ons, deodorant sticks, deodorant creams, products of
decorative cosmetics such as e.g. eyeshadows, nail varnishes,
make-ups, lipsticks, mascara, toothpaste, dental floss; hygiene
articles selected from candles, lamp oils, joss sticks,
insecticides, repellents, propellants, rust removers, perfumed
freshening wipes, armpit pads, baby diapers, sanitary towels,
toilet paper, cosmetic wipes, pocket tissues, dishwasher
deodorizer; cleaners for solid surfaces selected from perfumed
acidic, alkaline and neutral cleaners, such as e.g. floor cleaners,
window cleaners, dishwashing detergents, bath and sanitary
cleaners, scouring milk, solid and liquid toilet cleaners, powder
and foam carpet cleaners, waxes and polishes such as furniture
polishes, floor waxes, shoe creams, disinfectants, surface
disinfectants and sanitary cleaners, brake cleaners, pipe cleaners,
limescale removers, grill and oven cleaners, algae and moss
removers, mold removers, facade cleaners; textile detergents
selected from liquid detergents, powder detergents, laundry
pretreatments such as bleaches, soaking agents and stain removers,
fabric softeners, washing soaps, washing tablets.
According to a further aspect, the fragrances used according to the
invention and the fragrance compositions according to the invention
are suitable for use in surfactant-containing perfumed articles.
This is because fragrances and/or fragrance compositions with a
musk note and pronounced naturalness are often sought--especially
for the perfuming of surfactant-containing formulations such as,
for example, cleaners (in particular dishwashing compositions and
all-purpose cleaners).
According to a further aspect, fragrances used according to the
invention and fragrance compositions according to the invention can
be used as agents for providing (a) hair or (b) textile fibers with
a rosy odor note.
The fragrances to be used according to the invention and fragrance
compositions according to the invention are therefore particularly
well suited for use in surfactant-containing perfumed articles.
It is preferred if the perfumed article is one of the following: an
acidic, alkaline or neutral cleaner which is selected in particular
from the group consisting of all-purpose cleaners, floor cleaners,
window cleaners, dishwashing detergents, bath and sanitary
cleaners, scouring milk, solid and liquid toilet cleaners, powder
and foam carpet cleaners, liquid detergents, powder detergents,
laundry pretreatments such as bleaches, soaking agents and stain
removers, fabric softeners, washing soaps, washing tablets,
disinfectants, surface disinfectants, an air freshener in liquid
form, gel-like form or a form applied to a solid carrier or as an
aerosol spray, a wax or a polish, which is selected in particular
from the group consisting of furniture polishes, floor waxes and
shoe creams, or a body care composition, which is selected in
particular from the group consisting of shower gels and shampoos,
shaving soaps, shaving foams, bath oils, cosmetic emulsions of the
oil-in-water type, of the water-in-oil type and of the
water-in-oil-in-water type, such as e.g. skin creams and lotions,
face creams and lotions, sunscreen creams and lotions, aftersun
creams and lotions, hand creams and lotions, foot creams and
lotions, hair removal creams and lotions, aftershave creams and
lotions, tanning creams and lotions, hair care products such as
e.g. hairsprays, hair gels, setting hair lotions, hair
conditioners, permanent and semipermanent hair colorants, hair
shaping compositions such as cold waves and hair smoothing
compositions, hair tonics, hair creams and hair lotions, deodorants
and antiperspirants such as e.g. underarm sprays, roll-ons,
deodorant sticks, deodorant creams, products of decorative
cosmetics.
Ingredients with which fragrances used according to the invention
or fragrance compositions according to the invention can preferably
be combined are, for example: preservatives, abrasives, antiacne
agents, agents to combat skin aging, antibacterial agents,
anticellulite agents, antidandruff agents, anti-inflammatory
agents, irritation-preventing agents, irritation-alleviating
agents, antimicrobial agents, antioxidants, astringents,
sweat-inhibiting agents, antiseptics, antistatics, binders,
buffers, carrier materials, chelating agents, cell stimulants,
cleaning agents, care agents, hair removal agents, surface-active
substances, deodorizing agents, antiperspirants, emollients,
emulsifiers, enzymes, essential oils, fibers, film formers,
fixatives, foam formers, foam stabilizers, substances for
preventing foaming, foam boosters, fungicides, gelling agents,
gel-forming agents, hair care agents, hair shaping agents, hair
smoothing agents, moisture-donating agents, moisturizing
substances, humectant substances, bleaching agents, strengthening
agents, stain removal agents, optical brighteners, impregnating
agents, soil repellents, friction-reducing agents, lubricants,
moisturizing creams, ointments, .degree. pacifiers, plasticizers,
covering agents, polish, shine agents, polymers, powders, proteins,
refatting agents, exfoliating agents, silicones, skin-calming
agents, skin-cleansing agents, skin care agents, skin-healing
agents, skin lightening agents, skin-protective agents,
skin-softening agents, cooling agents, skin-cooling agents, warming
agents, skin-warming agents, stabilizers, UV-absorbent agents, UV
filters, detergents, fabric softeners, suspending agents,
skin-tanning agents, thickeners, vitamins, oils, waxes, fats,
phospholipids, saturated fatty acids, mono- or polyunsaturated
fatty acids, .alpha.-hydroxy acids, polyhydroxy fatty acids,
liquefiers, dyes, color-protection agents, pigments,
anticorrosives, aromas, flavorings, fragrances, polyols,
surfactants, electrolytes, organic solvents or silicone
derivatives.
According to a further aspect, the fragrances are used in the
production of the perfumed articles in liquid form, undiluted or
diluted with a solvent or in the form of a fragrance composition.
Suitable solvents for this purpose are e.g. ethanol, isopropanol,
diethylene glycol monoethyl ether, glycerol, propylene glycol,
1,2-butylene glycol, dipropylene glycol, diethyl phthalate,
triethyl citrate, isopropyl myristate, etc. If the specified
solvents have their own olfactory properties, they are assigned
exclusively to the constituent "solvent" and not to the
"fragrances".
The fragrances and/or fragrance compositions present in the
perfumed articles according to the invention can in this
connection, in one embodiment, be absorbed onto a carrier, which
ensures both fine distribution of the fragrance or fragrance
composition within the product and controlled release upon use.
Carriers of this type may be porous inorganic materials such as
light sulfate, silica gels, zeolites, gypsums, clays, clay
granules, aerated concrete, etc. or organic materials such as woods
and cellulose-based materials.
The fragrances used according to the invention and the fragrance
compositions according to the invention can also be in
microencapsulated form, spray-dried form, in the form of inclusion
complexes or in the form of extrusion products and be added in this
form to the product or article to be perfumed. The properties can
be further optimized by so-called "coating" with suitable materials
with regard to a more targeted release of the scent, for which
purpose preferably waxy synthetic substances such as e.g. polyvinyl
alcohol are used.
The microencapsulation can take place for example by the so-called
coacervation method with the help of capsule materials, e.g. made
of polyurethane-like substances or soft gelatin. The spray-dried
perfume oils can be produced for example by spray-drying an
emulsion or dispersion comprising the perfume oil, wherein carrier
substances that can be used are modified starches, proteins,
dextrin and vegetable gums. Inclusion complexes can be prepared
e.g. by introducing dispersions of fragrance compositions and
cyclodextrins or urea derivatives into a suitable solvent, e.g.
water. Extrusion products can be produced by melting fragrances
used according to the invention and fragrance compositions
according to the invention with a suitable wax-like substance and
by extrusion with subsequent solidification, optionally in a
suitable solvent, e.g. isopropanol.
c3) Preparation of Fragrances According to the Invention
The carbaldehydes according to the invention of the formula X
##STR00012## in which A is as defined above and is a cyclic
C.sub.13 to C.sub.17 radical, in particular C.sub.13-, C.sub.15-,
or C.sub.17 radical, are obtainable starting from cyclic ketones or
cyclic olefin starting materials known per se.
The following synthesis routes are described in more detail by way
of example to further illustrate the invention:
Synthesis Route 1: Carbaldehyde Synthesis by N.sub.2O Oxidation
Starting from the corresponding, aliphatic carbocycle, in
particular a cyclic mono- or polyunsaturated olefin XI (i.e.
compared to the cyclic radical A in the product of the formula X,
the starting compound XI comprises an additional C.dbd.C double
bond and an additional carbon atom in the ring), compounds of the
formula X are accessible by dinitrogen monoxide oxidation, as
described e.g. in WO2010/086313.
An example of a suitable starting compound (which can be used both
in stereoisomerically pure form as well as in the form of
stereoisomer mixtures) for the preparation of compounds of the
formula (X), in which A is a monounsaturated C.sub.15 radical, is
cyclohexadeca-1,9-diene, which is either commercially available or
can be prepared according to example 2 of WO 2012/084673 or in
accordance with EP-A-1 288 181.
In particular here, a cyclic olefin is oxidized by reaction with
dinitrogen monoxide. Dinitrogen monoxide here can be used in pure
form or optionally in a mixture with other substances gaseous under
reaction conditions, such as e.g. carbon dioxide, for dilution.
In this connection, the reaction of the cyclic olefin with
dinitrogen monoxide can take place without a diluent or in the
presence of at least one suitable solvent or diluent. Preferably,
the reaction takes place without a diluent. Essentially all
customary solvents and/or diluents are suitable here, but with the
proviso that they have neither a C--C double bond nor a C--C triple
bond, nor an aldehyde group. Suitable solvents to be mentioned
include: cyclic alkanes, for example cyclohexane, cyclopentane,
cyclooctane, cyclododecane or saturated aliphatic or aromatic,
optionally alkyl-substituted hydrocarbons.
The temperature during the reaction is e.g. 140 to 350.degree. C.,
such as in particular 180 to 320.degree. C. or 200 to 300.degree.
C. It is also possible to carry out the reaction at two or more
temperatures or in two or more temperature ranges which are in each
case within the limits stated above. Temperature changes in the
course of the reaction can be completed continuously or else
discontinuously. In particular, however, the reaction temperature
is essentially constant.
The pressure during the reaction of the cyclic olefin with
dinitrogen monoxide is in particular higher than the intrinsic
pressure of the starting material or product mixture at the
selected reaction temperature or the selected reaction
temperatures. The pressure is e.g. 1 to 1000 bar, such as e.g. 40
to 300 bar or 50 to 200 bar.
It is possible to carry out the reaction of the cyclic olefin with
dinitrogen monoxide at two or more pressures or within two or more
pressure ranges which are in each case within the limits stated
above. Pressure changes in the course of the reaction can be
completed continuously or else discontinuously. In particular,
however, the pressure during the reaction is essentially
constant.
As regards the reactors that can be used for the reaction (in the
laboratory--or production scale), there are no particular
limitations. In particular, the reaction can take place in a batch
procedure or continuous procedure. Consequently, examples of
reactors that can be used are at least one CSTR (Continuous Stirred
Tank Reactor) with at least one internal and/or at least one
external heat exchanger, at least one tubular reactor, at least one
tube-bundle reactor or at least one loop reactor. It is likewise
possible to configure at least one of these reactors in such a way
that it has at least two different zones. Such zones can differ for
example in reaction conditions such as, for example, the
temperature or the pressure and/or in the geometry of the zone,
such as, for example, the volume or the cross section. If the
reaction is carried out in two or more reactors, two or more
identical reactor types or at least two different reactor types can
be used. In particular, the reaction with dinitrogen monoxide is
carried out in a single reactor. For example, the reaction can take
place in a continuous procedure or in a batch procedure.
The residence time of the reaction mixture in the reactor is
generally in the range from 0.1 to 40 hours, preferably in the
range from 1 to 30 hours, further preferably in the range from 2 to
25 hours.
In the feed, the molar ratio of dinitrogen monoxide and the cyclic
olefin is generally in the range from 0.01 to 30, such as e.g. in
the range from 0.03 to 10, particularly preferably in the range
from 0.05 to 1 and very particularly preferably in the range from
0.08 to 0.2.
Since dinitrogen monoxide is preferably used in deficit, only some
of the cyclohexadeca-1,9-diene (XI) is reacted. Unreacted
cyclohexadeca-1,9-diene is separated from the reaction product by
distillation and returned again to the reaction. Here, the
unreacted cyclohexadeca-1,9-diene is produced as top product and
the reaction product is produced as bottom product of the column.
The distillation takes place here at a top pressure of 20 mbar and
a bottom temperature of 210.degree. C. The pressure difference over
the column was 18 mbar. The column was equipped with structured
fabric packing of the Montz A3 type. The packing height was 4 m and
the feed was at 2 m. The compound X was then isolated from the
resulting bottom discharge by distillation as secondary component
(see example 1).
The desired reaction product is produced here as secondary
component, meaning that the reaction mixture has to be purified in
a suitable manner. This can take place e.g. by distillation (such
as in particular by fractional distillation, preferably at reduced
pressure) or chromatographically. Suitable purification methods are
known to the person skilled in the art. The purification can take
place e.g. batchwise or else continuously.
For example, the distillation by means of distillation column with
packings known to the person skilled in the art can be used. The
optimum distillation conditions can be ascertained by the person
skilled in the art without unreasonable effort. The distillation
can be carried out in particular in vacuo, for example at a
pressure <1000 mbar, <500 mbar, <300 mbar, <100 mbar or
<10 mbar. The distillation column used can have a plurality of,
such as e.g. at least 20, at least 25 or at least 30, theoretical
plates, such as e.g. up to 70 plates. The reflux ratio can be e.g.
in the range from about 5 to 100 and can be at least 20, at least
25 or at least 30 and is in particular about 100 for a particularly
advantageous fractionation.
For example, a column chromatography can also take place instead of
or following a distillative purification. For this, column
materials and eluents known to the person skilled in the art are
used. The optimum chromatography conditions, such as column
geography and rate of eluent, can be ascertained by the person
skilled in the art without unreasonable effort.
Examples of suitable column materials are polar adsorption agents
such as e.g. iron oxide Fe.sub.2O.sub.3, aluminum oxide,
carbohydrates or silica gel with or without additives such as e.g.
fluorescence indicators or gypsum.
Examples of suitable eluents are: aliphatic or aromatic eluents,
such as e.g. alkanes or cycloalkanes, such as e.g. pentane,
petroleum ether, hexane, heptane, toluene or the corresponding
cyclic compounds; aliphatic ethers, esters, such as e.g. Et.sub.2O,
MTBE, EtOAc, acetone, or mixtures of such eluents, such as e.g.
hexane/MTBE, hexane/EtOAc, pentane/Et.sub.2O, petroleum
ether/Et.sub.2O.
In this process, a desired carbaldehyde of the formula X, or
mixtures thereof, can be isolated in pure form or in a purity of
more than 20, such as e.g. more than 30, more than 40, more than
50, more than 60, more than 60 or more than 80% by weight.
The carbaldehyde of the formula X can be isolated here in
stereoisomerically pure form, or in particular as a mixture of two
or more stereoisomers, particularly if radical A has a C.dbd.C
double bond.
In particular, aromatic substances comprising trans- and
cis-cyclopentadec-8-enylcarbaldehyde (I, III) and/or
trans-cyclopentadec-7-enylcarbaldehyde (II) are accessible by this
route.
Synthesis Route 2: Multistage Carbaldehyde Synthesis Via Wolff
Rearrangement
Starting from the corresponding, cycloaliphatic aldehyde, in
particular a cyclic mono- or polyunsaturated ketone XII (i.e.
compared to the cyclic radical A in the product of the formula X,
starting compound XII comprises an additional ring carbon atom),
compounds of the formula X are accessible in a multistage process.
The individual synthesis stages are known per se to the person
skilled in the art in the field of organic synthesis.
Examples of suitable starting compounds (which can be used both in
stereoisomerically pure form as well as in the form of stereoisomer
mixtures) for the preparation of compounds of the formula (X), in
which A is a monounsaturated C.sub.15 radical, comprise
Globanone.RTM., as available e.g. from Symrise.
a) Stage 1: Formylketone Preparation
Corresponding reactions are described e.g. in: Wu, Z.; Li, Y.; Cai,
Y.; Yuan, J.; Yuan, C., Bioorganic & Medicinal Chemistry
Letters 2013, 23, 4903-4906; or Prelog, V.; Ruzieka, L.; Metzler,
O, HELV. CHIM. ACTA 1947, 30, 1883-1895.
A suitable reaction vessel with reflux condenser is charged, under
an inert gas atmosphere, with a suspension of a suitable hydride
such as e.g. NaH, in organic phase, such as e.g. DMF. At reduced
temperature, such as e.g. 0 to 10.degree. C., a solution of the
cycloaliphatic ketone, such as e.g. of the monounsaturated cyclic
C.sub.16 ketone globanone (XII), is added dropwise to this
suspension, e.g. over a period of 1 to 5 hours. The ketone is used
in an approximately equimolar amount, but in particular in a slight
(e.g. 1.1- to 1.5-fold) molar deficit, based on the hydride. To
complete the deprotonation, the temperature can be increased and
the reaction mixture can be held at this temperature over a
suitable time period, e.g. for the period from 1 to 4 h at 40 to
80.degree. C., such as e.g. 2 h at 60.degree. C. The reaction
mixture is then cooled again, e.g. to 0 to 10.degree. C. The
addition of a solution of methyl formate in a suitable solvent,
such as e.g. DMF, then takes place. Methyl formate is used in an
approximately equimolar amount, but in particular in a slight (e.g.
1.1- to 1.5-fold) molar excess, based on the ketone. The reaction
mixture is stirred over a suitable period, such as e.g. 5 to 30 h,
such as e.g. about 16 h at ambient temperature, and the reaction is
then ended by adding ice-water. The mixture is washed with ether,
e.g. MTBE, and the organic phases are discarded. By adding sulfuric
acid, the aqueous phase is acidified, e.g. to pH 2, and extracted
several times with ethyl acetate. The combined ethyl acetate phases
are dried over Na.sub.2SO.sub.4 and then concentrated in vacuo. The
residue thus obtained consists predominantly of the desired
regioisomeric formyl ketones XIII or the tautomeric enols thereof
and is used without further work-up in the subsequent stage.
b) Stage 2: Diazoketone Preparation
Corresponding reactions are described e.g. in Regitz, M. and Ruter,
J., Chem. Ber. 1968, 101, 1263-1270.
Added dropwise with cooling, e.g. to -20 to 0.degree. C., in
particular at -10.degree. C. over a period of several hours, such
as e.g. 2 to 8 h, to a solution, charged to a suitable reaction
vessel, of the crude product from preceding stage 1 and
triethylamine (in particular in molar excess, such as e.g. 1.5- to
2-fold excess) in a suitable solvent, in particular in a
halogenated hydrocarbon, such as dichloromethane, is a solution of
4-acetamidobenzyl azide (in molar excess, such as e.g. 1.5- to
2-fold excess) in the same solvent. In principle, other diazo
transfer reagents are also suitable, such as toluenesulfonyl azide.
Optionally after leaving the reaction mixture to stand at elevated
temperature, such as e.g. room temperature, and solvent exchange
(e.g. dichloromethane for MTBE), the organic phase is washed with
sodium hydroxide solution and the aqueous phase is extracted twice
with the organic solvent, e.g. MTBE. The combined organic phases,
comprising the desired diazo ketone XIV (optionally as isomer
mixture), are dried over Na.sub.2SO.sub.4 and further reacted as
described below.
c) Stage 3: Wolff Rearrangement and Esterification of the Ketene
Formed Therein:
Corresponding reactions are described e.g. in Regitz, M. and Ruter,
J., Chem. Ber. 1968, 101, 1263-1270, or Kirmse, W., Eur. J. Org.
Chem. 2002, 14, 2193-2256.
A solution of the diazo ketone XIV from stage 2 is slowly added
dropwise over a period of 5 to 20 h, such as e.g. 10 h, to heated
alkanol, such as e.g. heated 1-hexanol (e.g. 150.degree. C.),
charged to a reaction vessel provided with distillation bridge.
With controlled N.sub.2-formation, the organic solvent is
simultaneously removed by distillation. At the end of the evolution
of gas, the reaction mixture is cooled and then remains of solvent
and alkanol are removed in vacuo, giving the desired cyclic ester
XV with an aliphatic ring smaller by 1 carbon atom (optionally in
the form of an isomer mixture).
d) Stage 4: Ester Reduction to the Alcohol
Corresponding reactions are described e.g. in March, J. "Advanced
organic Chemistry", 4th edition, John Wiley & Sons, New York
1992.
A reducing agent, e.g. a solution of diisobutylaluminum hydride
(DIBAL-H) in molar excess (e.g. 1.5- to 3-fold), is added dropwise
to a solution of the ester XV from stage 3 in an inert, organic
apolar solvent, such as e.g. toluene, charged to a chilled reaction
vessel, e.g. at -78.degree. C. The cooling is removed and after
leaving to stand at ambient temperature, the reaction is ended,
such as e.g. by adding ethyl acetate and a saturated aqueous K,Na
tartate solution. The aqueous phase is extracted with ethyl
acetate, the combined organic phases are dried over
Na.sub.2SO.sub.4 and are concentrated in vacuo, giving the
corresponding cyclic alcohols XVI (optionally in the form of an
isomer mixture).
e) Stage 5: Alcohol Oxidation to the Carbaldehyde:
Corresponding reactions are described e.g. in March, J. "Advanced
organic Chemistry", 4th edition, John Wiley & Sons, New York
1992.
In succession, kieselguhr and an oxidizing agent suitable for
primary alcohols, such as e.g. HOCl, pyridinium dichromate or in
particular pyridinium chlorochromate (PCC) (in approximately
equimolar amounts), are added to a solution of the reaction product
from stage 4 in a suitable solvent, such as e.g. dichloromethane.
Following reaction for several hours, e.g. 3-6 h at ambient
temperature, the reaction mixture is filtered over silica gel and
concentrated in vacuo. This gives the desired aldehyde X
(optionally in the form of an isomer mixture).
e) Stage 6 (Optional) Column Chromatography
For this, column materials and eluents known to the person skilled
in the art are used. The optimum chromatography conditions, such as
column geometry and rate of eluent, can be ascertained by the
person skilled in the art without unreasonable effort.
Examples of suitable column materials are polar adsorption agents
such as e.g. iron oxide Fe.sub.2O.sub.3, aluminum oxide,
carbohydrates or silica gel with or without additives such as e.g.
fluorescence indicators or gypsum.
Examples of suitable eluents are: aliphatic or aromatic eluents,
such as e.g. alkanes or cycloalkanes, such as e.g. pentane,
petroleum ether, hexane, heptane, toluene or the corresponding
cyclic compounds; aliphatic ethers, esters or ketones, such as e.g.
MTBE, Et.sub.2O, EtOAc or acetone, or mixtures of such eluents such
as e.g. hexane/MTBE, hexane/EtOAc, pentane/Et.sub.2O, petroleum
ether/Et.sub.2O.
In the process, a desired carbaldehyde, or mixtures thereof, can be
isolated in pure form or in a purity of more than 20, such as e.g.
more than 30, more than 40, more than 50, more than 60, more than
60 or more than 80% by weight.
The carbaldehyde can be present here in stereoisomerically pure
form, or in particular as a mixture of two or more
stereoisomers.
In particular, aromatic substances comprising
trans-cyclopentadec-8-enylcarbaldehyde (I) and/or
cis-cyclopentadec-8-enylcarbaldehyde (III), and/or
trans-cyclopentadec-7-enylcarbaldehyde (II), in particular ternary
mixtures thereof, are accessible by this route.
The invention will now be explained in more detail by reference to
the following nonlimiting working examples:
EXPERIMENTAL SECTION
Methods:
Gas Chromatography (GC)
Separating column: CP-Wax 52CB 25 m.times.0.32 mm.times.1.2 .mu.m 1
ml/min N.sub.2
Conditions: 90.degree.-5 min-10.degree./min-240.degree.-30 min
Inj/Det 200.RTM./250.degree. (method A)
Conditions: 80.degree.-3.degree./min-250.degree.-Inj/Det
200.degree./250.degree. (method B) (only example 2)
Sample volume: 0.2 ml
GC/MS
Separating column: CP-Wax 52 CB (1.2 .mu.m film thickness),
splitting ratio 10:1
Conditions: 80.degree.-3 min-240.degree.-30 min 0.2 .mu.l
MS conditions: 25-785 amu, 70 eV
GC/IR
Detector: MCT/A wavelength 650-4000 cm.sup.-1
Cell/transfer temperature 250.degree. C.
Scan 6
Resolution 8
Column Chromatography
A glass column with fritte base was used. The column was packed to
2/3 with slurried silica gel F.sub.254. The solvent mixture was
pushed through the column at a superatmospheric pressure of 0.2-0.4
bar.
Example 1: C.sub.15-Aldehyde Synthesis by N.sub.2O Oxidation of
1,9-Cyclohexadecadiene
In an adiabatic tubular reactor (3 m in length, diameter 6 cm,
reactor volume 9 l) filled with Raschig rings made of 1.4541
stainless steel, 2000 g/h of 1,9-cyclohexadecadiene
(cis/trans-isomer mixture) were reacted with 52 ml/h an
N.sub.2O/CO.sub.2 mixture (15% CO.sub.2 fraction) at a reactor feed
temperature of 216.degree. C. Molar ratio olefin/N.sub.2O: 9-10.
Unreacted 1,9-cyclohexadecadiene was separated off distillatively
by means of a distillation column (Montz fabric packing A3,
separation-effective height 4000 mm, internal diameter 55 mm, feed
at half height of the column) at a bottom temperature of
210.degree. C. and a top pressure of 20 mbar. The bottom discharge
comprises approx, 5% by weight of the C.sub.15-aldehydes (I)
(t.sub.Ret=23.3 min GC method A), (II) (t.sub.Ret=23.7 min) and
(III) (t.sub.Ret=24.1 min) and less than 1% by weight of
1,9-cyclohexadecadiene (t.sub.Ret=18.2, 18.5, 18.9 min; 3 isomers)
(main component in the bottom is globanone; t.sub.Ret=24.4, 24.8
min, 2 isomers).
Example 2 C.sub.15-Aldehyde Synthesis by N.sub.2O Oxidation of
1,9-Cyclohexadecadiene
A mixture consisting of cyclohexadeca-1,9-diene (isomer mixture,
sum of the isomers approx. 98%, 20 g) and cyclohexane (80 g) was
mixed in a 300 ml autoclave. The autoclave was sealed and
compressed with nitrogen to 50 bar and then decompressed again. The
process was repeated three times. After the last decompression, the
autoclave was compressed with N.sub.2O to 30 bar, molar ratio
olefin/N.sub.2O 250-270, then the stirrer was switched on (at 400
rpm) and the autoclave was heated to the reaction temperature over
the course of an hour. The mixture was stirred for 12 h at
220.degree. C. The system was then cooled to room temperature, the
autoclave was decompressed and the crude discharge analyzed by GC.
In total, the discharge comprised 2,2% by weight of
trans-cyclopentadec-8-enylcarbaldehyde (I) (t.sub.Ret=23.3 min),
trans-cyclopentadec-7-enylcarbaldehyde (II) (t.sub.Ret=23.7 min)
and cis-cyclopentadec-8-enylcarbaldehyde (III) (t.sub.Ret=24.1
min).
Example 3: Enrichment of C.sub.15-Aldehydes by Fractional
Distillation
2600 g of a mixture (crude discharge from oxidation of
cyclohexadeca-1,9-diene with N.sub.2O; see example 1) with in total
approx. 5% trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (III) were fractionally
distilled in a batch column (Sulzer fabric packing DX,
separation-effective height 2000 mm, diameter 43 mm, top pressure:
5 mbar, pressure loss over column: 5 mbar, bottom temperature:
180.degree. C., Sambay evaporator, reflux ratio: 100). The mixture
of trans-cyclopentadec-8-enylcarbaldehyde (I) (t.sub.Ret=23.3 min),
trans-cyclopentadec-7-enylcarbaldehyde (II) (t.sub.Ret=23/min) and
cs-cyclopentadec-8-enylcarbaldehyde (III) (t.sub.Ret=24.1 min) was
able to be enriched in the process in different fractions to 29, 33
and 46% by weight. The respective content was determined by gas
chromatography (boiling point of the fractions 160, 167 and
167.degree. C.)
Example 4: Purification by Column Chromatography
2.05 g of a mixture of trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (III) with a content total of
33% by weight (cf. example 3) were purified by means of column
chromatography (silica gel, glass column with fritte base,
superatmospheric pressure of 0.2 bar) using an eluent mixture of
cyclohexane/MTBE (50:1 and 40:1). Following chromatographic
purification, 100 mg of trans-cyclopentadec-8-enylcarbaldehyde (I)
(t.sub.Ret=23.494 min) were isolated with a purity of 83%.
##STR00013##
.sup.1H NMR (500 MHz, CDCl.sub.3, 25.degree. C.): .sigma.=9.5 (s,
CHO, 1H), 5.4-5.3 (m, HC.dbd.CH, 2H), 2.4-2.3 (m, 1H), 2.2-1.9 (m,
4H), 1.7-1.6 (m, 2H), 1.5-1.1 (m, 18H).
.sup.13C-NMR (125 MHz, CDCl.sub.3, 25.degree. C.): .sigma.=206.0
(C.dbd.O), 131.2 (HC.dbd.CH), 48.4 (CH), 31.6 (2.times.CH.sub.2),
28.3 (2.times.CH.sub.2), 27.0 (2.times.CH.sub.2), 26.7
(2.times.CH.sub.2), 26.6 (2.times.CH.sub.2), 25.1
(2.times.CH.sub.2).
IR (GC/IR) .upsilon. [cm.sup.-1]=3029 (1,2 trans subst. DB), 2934,
2865, 2797, 2695, 1738 (CHO), 1454, 1353, 1110, 968 (1,2 trans
subst. DB).
Example 5; C15-Aldehyde Synthesis Via Wolff Rearrangement
a) Stage 1:
##STR00014##
In a three-necked flask with reflux condenser and mechanical
stirrer, NaH (60% by weight in mineral oil, 33.5 g, 0.84 mol, 1.1
eq.) is introduced under an argon atmosphere and suspended in DMF
(DMF=N,N-dimethylformamide, 50 ml). At 0.degree. C., a solution of
globanone (1, 150 g, 0.64 mol, 1.3 eq.) in dry DMF (250 ml) is
added dropwise to this suspension over a period of 3.5 h. To
complete the deprotonation, the mixture is heated at 60.degree. C.
for 2 h and then cooled to 0.degree. C. After adding a solution of
methyl formate (57 g, 0.95 mol, 1.5 eq.) in DMF (50 ml), the
mixture is stirred for 16 h at ambient temperature and the reaction
is then ended by adding ice-water. The mixture is washed twice with
MTBE (MTBE: Methyl tert-butyl ether) and the organic phases are
discarded. The aqueous phase is brought to pH 2 by adding sulfuric
acid (50% strength by weight) and extracted several times with
ethyl acetate. The combined ethyl acetate phases are dried over
Na.sub.2SO.sub.4 and then concentrated in vacuo. The residue thus
obtained (134 g) consists, according to NMR, to about 90% of the
desired regioisomeric formyl ketones 2a and 2b and/or the
tautomeric enols thereof (2c-2f) and is used without further
work-up in the subsequent stage.
b) Stages 2 and 3:
##STR00015##
At -10.degree. C., a solution of 4-acetamidobenzyl azide (97.3 g,
0.41 mol, 0.9 eq.) in dichloromethane (400 ml) is added dropwise to
a solution of the crude product (2a-f) from the preceding stage 1
(134 g purity about 90%, 0.46 mol, 1 eq.) and triethylamine (86.6
g, 0.86 mol, 1.9 eq.) in dichloromethane (100 ml) over a period of
4 h. After 20 h at RT, MTBE (400 ml) is added and the
dichloromethane is distilled off. The organic phase is washed with
sodium hydroxide solution (6% by weight) and the aqueous phase is
extracted twice with MTBE. The combined MTBE phases are dried over
Na.sub.2SO.sub.4 and further reacted as described below.
##STR00016##
The solution of the diazoketone 3 in MTBE is slowly added dropwise
over a period of 10 h to 1-hexanol (300 ml) heated to 150.degree.
C. such that the N.sub.2 formation remains controllable and at the
same time the introduced MTBE can be distilled off continuously via
a distillation bridge. At the end of the gas evolution, the
reaction mixture is cooled and then remains of MTBE and the
1-hexanol are removed in vacuo. This gives 92 g of a yellow,
viscous residue which, according to NMR, comprises 60-70% of the
esters 4a and 4b as isomer mixture.
c) Stage 4:
##STR00017##
At -78.degree. C., a solution of diisobutylaluminum hydride
(DIBAL-H) in heptane (c=1 mol/l, 490 ml, 0.5 mol, 2.5 eq.) is added
dropwise to a solution of the ester (4a and 4b) (92 g, 70% purity,
0.2 mol, 1 eq.) in toluene (130 ml). The cooling is removed and,
after 2 h at ambient temperature, the reaction is ended by adding
ethyl acetate (50 ml) and saturated aqueous K,Na tartrate solution
(400 ml). The suspension is stirred until the clouding has cleared
at room temperature. The aqueous phase is extracted with ethyl
acetate, the combined organic phases are dried over
Na.sub.2SO.sub.4 and concentrated in vacuo. 77 g of the isomeric
alcohols 5a and 5b are obtained as a colorless oil.
d) Stage 5:
##STR00018##
In succession, kieselguhr (30 g) and pyridinium chlorochromate
(PCC) (30 g, 0.14 mol, 1 eq.) are added to a solution of half of
the crude mixture from the preceding stage 4 (33 g, 0.14 mol, 1
eq.) in dichloromethane (300 ml). After 4 h at ambient temperature,
the reaction mixture is filtered over silica gel and concentrated
in vacuo. 21 g of the isomeric aldehydes 6a and 6b are obtained in
a purity of 70% (71 mmol, total yield over five stages starting
from globanone 22%).
To assess the olfactory properties, some of the crude product is
purified by column chromatography.
e) Stage 6 (Column Isolation I, II and III)
5.0 g of a mixture of the aldehydes 6a and 6b from stage 5 with a
content, according to GC, in total of 70% by weight were purified
by means of chromatography using an eluent mixture of
cyclohexane/MTBE (60:1-40:1). Following chromatographic
purification, 1 g of a mixture of
trans-cyclopentadec-8-enylcarbaldehyde (I),
trans-cyclopentadec-7-enylcarbaldehyde (II) and
cis-cyclopentadec-8-enylcarbaldehyde (Ill) was isolated with a
purity of 87% (total of (I)+(II)+(111) in the ratio 46:24:29).
f) Analytical Results:
##STR00019##
IR (GC/IR) .upsilon. [cm.sup.-1]=3023 (trans 1,2 subst. DB), 2934,
2864, 2801, 2696, 1738 (CHO), 1454, 968 (trans 1,2 subst. DB).
MS (GC/MS-IR coupling) m/z=236.
##STR00020##
IR (GC/IR) .upsilon. [cm.sup.-1]=3012 (1,2 cis subst., DB), 2935,
2866, 2801, 2698, 1738 (CHO), 1457, 719 (1,2 cis subst. DB).
MS (GC/MS-IR coupling) m/z=236.
NMR Data of the Mixture (II) and (III):
.sup.1H NMR (500 MHz, CDCl.sub.3, 25.degree. C.): .sigma.=9.6 (s,
2H, 2.times.CHO), 5.4-5.2 (m, 4H, 2.times.HC.dbd.CH), 2.5-1 (m,
50H).
.sup.13C-NMR (125 MHz, CDCl.sub.3, 25.degree. C.): .sigma.=205.4
(CHO), 205.3 (CHO), 131.4, 131.0, 130.2 (2.times.CH.sub.ar), 50.4
(CH.sub.alk), 49.9 (CH.sub.alk), 31.7-24.4 (24.times.CH.sub.2).
FIG. 1 shows the GC/IR spectra of the compounds I, II and III
according to the invention (referred to therein as components 1, 2
and 3).
Example 6: Olfactory Assessment
1) Assessment of Different Mixtures of the Aldehydes I, II and
III
Composition of the Investigated Samples:
No. 1: (I):(II):(III)=46:24:29; purity=87.5% (total (I-III)) (cf.
example 5, after stage 6)
No. 2: (I):(II):(III)=43:24:33; purity=77.8% (total (I-III))
Result
Sample No. 1: Smelling strip test <1 min musk Smelling strip
test 30 min musk Smelling strip test 1 h musk Smelling strip test
24 h musk
Sample No. 2: Smelling strip test <1 min musk (significantly
more intensive than sample No. 1) Smelling strip test 30 min musk
(significantly more intensive than sample No. 1) Smelling strip
test 1 h musk (significantly more intensive than sample No. 1)
Smelling strip test 24 h musk (significantly more intensive than
sample No. 1)
The mixtures of the aldehydes (I-III) have a musk-like odor
note.
2) Assessment of Aldehyde I;
Composition of the Sample
(I):(II):(III)=93:2:4; purity=89.4% (total (I-III)) (cf. example 4)
Result: Smelling strip test <1 min musk, considerably soapy,
green, gassy Smelling strip test 10 min musk, considerably soapy,
green, gassy Smelling strip test 30 min musk, considerably soapy,
green, gassy Smelling strip test 1 h musk, considerably soapy,
green, gassy Smelling strip test 24 h musk
The pure substance (I) also has a considerably soapy, green and
gassy odor besides the musk-like odor note.
Reference is made expressly to the disclosure of the documents
mentioned herein.
* * * * *